CN105612120A - LMFP cathode materials with improved electrochemical performance - Google Patents

LMFP cathode materials with improved electrochemical performance Download PDF

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Publication number
CN105612120A
CN105612120A CN201480051578.8A CN201480051578A CN105612120A CN 105612120 A CN105612120 A CN 105612120A CN 201480051578 A CN201480051578 A CN 201480051578A CN 105612120 A CN105612120 A CN 105612120A
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Prior art keywords
precursor
lithium
iron
mole
lmfp
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M·S·帕克特
M·M·奥尔肯
T·德累泽恩
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/377—Phosphates of heavy metals of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/39—Condensed phosphates of alkali metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

LMFP cathode materials are made in a mechanochemical/solid state process. The precursors are dried in a preliminary step to reduce the water content of the precursors of less than 1% by weight and preferably less than 0.25% by weight. The dried precursors are then dry milled and calcined to form particles of an olivine LMFP. The product has excellent specific capacity and capacity retention.

Description

There is the LMFP cathode material of improved chemical property
Technical field
The present invention relates to the method for olivine iron manganese phosphate for lithium cathode material and this type of material of manufacture of lithium battery.
Background technology
Lithium battery be widely used as vehicle and permitted eurypalynous electronic equipment once and secondary cell. These batteries usually haveHigh-energy and power density.
Known LiFePO4A kind of thermally-stabilised and there is hypotoxic lower cost materials. There is small grain size and good when makingWhen good carbon coating, it can also represent very high high rate performance (high power density). For those reasons, LiFePO4Have been found that the cathode material as lithium battery. But, LiFePO4(3.4V is to Li to have relatively low operating voltage+/Li)And because this point has the energy density low with respect to Oxide Cathode Materials. In principle, operating voltage and thereforeEnergy density can be by replacing some or all iron to produce olivine iron manganese phosphate for lithium (Li with manganeseaMnbFe(1-b)PO4，(LMFP)) negative electrode increases, and does not significantly sacrifice power capacity.
In fact, LMFP negative electrode not yet reaches its theoretical performance. This is owing to some factors, especially described materialLow intrinsic electron conductivity. In addition, occur via one dimension passage through the lithium transmission of olivine crystal structure, be subject to crystalline substanceImpurity in body structure blocks and defective effect. Another problem be LMFP electrode cycle performance of battery usually due toCirculation under capacitance loss and not ideal.
Therefore, need a kind of cost-efficient method for the preparation of the better LMFP cathode material of performance.
Assess the number of ways of manufacturing LMFP cathode material. Comprising various intermediate processings, sol-gel processAnd solid-state approach. In solid-state approach, stoichiometric mixture and the calcining of grinding solid precursor form LMFP material.Described method tends to form the macroparticle that surface area is little, and it is bad as cathode material performance.
In order to overcome this problem, solid-state approach has been modified to and has comprised mechanical and chemical activation step. Mechanical and chemical activation isUndertaken by ground solid precursor before calcining step. Pulverize and mixed-powder, welded, pulverize alsoAnd weld again, promote the even mixing of parent material. Also there are some reactions in parent material, but until grinding-material warpCalcining just obtains single-phase LMFP material.
Although there is the rear grinding steps of grinding steps and calcining, the LMFP that relies on mechanical and chemical activation/solid-state approach to produceMaterial still tends to produce the large secondary of signal portion. Described macroparticle usually has approximately tens of microns to hundreds of micro-The size of rice. The existence of these macroparticles slows down electronics and lithium transmission and the infringement cathode performance in cell cathode. DescribedMacroparticle also makes cathode material be difficult to form film. Battery electrode is usually by by cathode material film (adding adhesive)Be applied in the metal forming of serving as current-collector and manufacture. The macroparticle of cathode material may be greater than required cathodic coating thickness. ThisHinder cathode material to form equal one deck. In addition, may even puncture or tear metal foil layer compared with macroparticle.
Another problem is to use the LMFP cathode material of mechanical and chemical activation/solid-state approach manufacture usually still to have deficiencyCycle performance of battery.
Summary of the invention
Applicant finds, these problems substantially (if not completely) by before dry grinding step fromParent material is removed water and is overcome. Therefore, the present invention is a kind of mechanochemistry for the manufacture of LMFP cathode material/solid-stateMethod, described method comprises:
A) dry grinding water content is less than the mixture of the precursor particles of 1 % by weight, and described precursor particles comprises a certain amount ofAt least one lithium precursor, at least one manganese (II) precursor, at least one iron (II) precursor and at least one phosphate precursor, appointSelection of land carbonaceous material or its precursor and optionally have the doping metals precursor of fugitive anion, to provide every mole of phosphoric acid rootManganese (II), the iron (II) of ion 0.85 to 1.15 mole of lithium and 0.95 to 1.05 mole of combination of every mole of phosphoric acid radical ion and mixingAssorted metal; And
B) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
In certain embodiments, described method comprises:
A) dry at least one lithium precursor, at least one manganese (II) precursor, at least one iron (II) precursor and at least one of comprisingPhosphate precursor, optionally carbonaceous material or its precursor and optionally there is the precursor of the doping metals precursor of fugitive anionParticle, is less than 1 % by weight so that the water content of described precursor is reduced to;
B) mixture of a certain amount of dried precursor particle of dry grinding, to provide every mole of phosphoric acid radical ion 0.85 to 1.15Manganese (II), iron (II) and the doping metals of mole of lithium and 0.95 to 1.05 mole of combination of every mole of phosphoric acid radical ion; And
C) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
Because the large water gauge existing in precursor material in conventional method shows the combination water of iron (II) precursor, so be only dried iron(II) precursor is usually enough to remove in conjunction with water. Therefore, in another embodiment, the present invention comprises
A) dry grinding comprises a certain amount of at least one lithium precursor, at least one manganese (II) precursor, at least one anhydrous iron(II) precursor and at least one phosphate precursor, optionally carbonaceous material or its precursor and optionally there is mixing of fugitive anionThe precursor particles of assorted metal precursor, to provide every mole of phosphoric acid radical ion 0.85 to 1.15 mole of lithium and every mole of phosphoric acid rootManganese (II), iron (II) and the doping metals of 0.95 to 1.05 mole of combination of ion; And
B) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
Method of the present invention provides some beat all advantages in its different embodiment. A very important advantage isProduct does not basically contain very large particle. This increases the productive rate of useable products, and reduces or even eliminate in useThe front cost of removing those macroparticles from product.
The chemical property of LMFP cathode material is also unexpectedly improved aspect at least two. First, have byThe battery of the negative electrode that this LMFP negative electrode is made represents unusual high power capacity while operation under high rate discharge. Secondly, the moonThe performance of utmost point material is stable conventionally during circulating battery. As below confirmed, these improvement in performance are not easy to and produceIn thing, the relative shortage of macroparticle is relevant. In conventional method, manufacture and then sieve the LMFP power of removing macroparticleCannot equal the chemical property of LMFP material synthetic in applicant's method. Applicant's method seems to produce toolThere is the single-phase olivine material of unusual few crystal defect and impurity.
Brief description of the drawings
Graphic is the microphoto of the LMFP particle manufactured in background technology method described in below comparative sample A.
Detailed description of the invention
Dry grinding step of the present invention is to carry out in following dry type agitated medium grinder, as sand mill, ball mill,Grater, machinery merge grinder or colloid mill and/or lapping device. Ball mill is general preferred type. PrecursorBe to introduce with dry particles solid form, " being dried " means not exist liquid phase in this case. Medium grinder contains and grindsGrinding media, it can be such as pottery or metal bead, roller etc. Dry grinding step can be divided two or more sub-stepsSuddenly carry out. For instance, in the first sub-step, can use larger abrasive media to provide granularity for example 0.2To the fine gtinding product in 1 micrometer range. In the second sub-step, can use less abrasive media so that granularity is enteredOne step is for example decreased in the scope of 0.01 to 0.1 micron.
Dry grinding step is suitable to 0 to 250 DEG C, preferably 0 to 100 DEG C and more preferably enter at the temperature of 0 to 50 DEG COK. Conventionally, there is no need to heat precursor or grinder during grinding steps. The material of some heating conventionally find be byMechanism in abrasive media to precursor. The condition during dry grinding step of being typically chosen in is to avoid calcined precursors.
Dry grinding step can be carried out for example period of 5 minutes to 10 hours. The amount of dry grinding can be according to being used forThe energy of described method represents; For the amount of the grinding energy of dry grinding particle normally 10 to 12,000kWh/tInitial precursor and preferred < 2000kWh/t. The amount of these energy does not comprise the mechanical friction of the motor because driving grinderOr energy loss due to other mechanical loss occurring in milling apparatus.
During dry grinding step, reduce the granularity of precursor and evenly mix various precursors. The welding of particle, pulverizingWelding is usually seen again. During dry grinding step, can there are some precursors reaction. But, few oliveStone LMFP material is considered to form during this step. The loss of some fugitive anion and volatile reaction product is passableDuring occurring in this step, but in addition a large amount of loss occurrences of fugitive material in follow-up calcining step.
For the precursor of dry grinding step be grind and follow-up calcining step during reaction formation olivine LMFP orWherein exist in the situation of carbonaceous material or its precursor, form the material of the nano-complex of olivine LMFP and carbonaceous materialMaterial. The empirical formula of olivine LMFP can be LiaMnbFecDdPO4, wherein a is 0.85 to 1.15 numeral; b0.05 to 0.95; C is 0.049 to 0.95; D is 0 to 0.1; 2.75≤(a+2b+2c+dV)≤3.10, V isThe valence mumber of D, and D is the one or more metal ion being selected from lower: magnesium, calcium, strontium, cobalt, titanium, zirconium,Molybdenum, vanadium, niobium, nickel, scandium, chromium, copper, zinc, beryllium, lanthanum and aluminium.
In certain embodiments, the value of b be 0.5 to 0.9 and the value of a be 0.49 to 0.1. In other embodiments,The value of b be 0.65 to 0.85 and the value of a be 0.34 to 0.15.
LMFP precursor is with stoichiometric amount, with the identical mol ratio in product olivine LMFP material provide lithium,The amount of iron (II), manganese (II), doping metals and phosphate anion provides. Carbonaceous material or its precursor are generally receive gainedRice compound contains 30% carbonaceous material, the preferred amount of 10 % by weight carbonaceous materials at the most at the most to be provided.
In certain embodiments, the water content of precursor is less than 1 % by weight. Water content comprises various precursor materials, and (it is commonBe salt and in some cases, moisture absorption slightly) in any combination water that may exist. If these are deposited in conjunction with waterBe in one or more precursor materials, so wherein some or all should optionally be removed so that the water content of precursor subtractsLittle of being less than 1 % by weight.
Before the water of precursor, body burden is preferably less than 0.25 % by weight, is more preferably less than 0.1 % by weight, is more preferably less than 0.025% by weight and be even more preferably less than 0.01 % by weight
As the water content of represented above precursor is applicable to whole precursors, but not indivedual precursor. If all combination of precursorsTotal moisture content be less than 1 percentage by weight, the water content of one or more indivedual precursors can be 1 percentage by weight soOr more.
Iron (II) precursor especially tends to contain in conjunction with water. Preferred iron (II) precursor is for example ethanedioic acid iron (II), and it contains conventionallyThere are two in conjunction with water. Ethanedioic acid iron (II) dihydrate is containing the water of the 15-20 % by weight of having an appointment. Therefore, remove from iron (II) precursorUsually be enough to make the water content that combines precursor to be reduced to essential level in conjunction with water.
In certain embodiments, some or all that remove iron (II) precursor are in conjunction with water, make iron (II) precursor anhydrous or almostAnhydrous. Use anhydrous iron (II) precursor or remove the replacement of at least some iron in conjunction with water (II) precursor and carry the normally iron in conjunction with water(II) precursor is usually enough to make the overall water content of precursor to be less than 1 % by weight. Therefore, in some embodiments of the invention,Iron (II) precursor is anhydrous ethanedioic acid iron (II). In other embodiments, iron (II) precursor contain every mole of precursor 0.0001 to0.25 mole in conjunction with water.
Having minimizing (comprising zero) can prepare by dried precursor material in conjunction with iron (II) precursor of water. Therefore, at thisIn some embodiment of invention, before dry grinding step, iron (II) precursor is prepared to drying steps. Except some orAll, in conjunction with outside water, free water also can be removed during drying steps.
Other precursor material also can contain the combination water of minimizing or not contain in conjunction with water. Any in other precursor material orAll can be dry in preparation drying steps before dry grinding step. As iron (II) precursor, substitute or except combinationOutside water, free water also can be removed from these other precursor materials.
In the time preparing drying steps, precursor can be separately or whole appointing together or with any two or more precursorsWhat sub-portfolio form is dry. In certain embodiments, precursor is will to be blended in one for the ratio of dry grinding step with itRise, and drying composite.
Drying steps is to carry out under high temperature and/or subatmospheric pressure condition. In the time using high temperature, temperature should be not highTo being enough to calcined precursors or being decomposed (except removing water). The temperature of 20 to 250 DEG C is suitable. 100 to 250 DEG CTemperature be preferred. Preferred temperature is 100 to 200 DEG C. If use subatmospheric pressure, press soPower can be for example 0.001 to 100kPa, preferably 0.001 to 10kPa.
Continue drying steps, until the water content of precursor is reduced to level as above. Several minutes consuming time of this possibilityTo a few hours, depend on water content and the other factors of equipment, temperature, pressure, parent material. Dry can continuation directlyTill reaching constant weight, usually indicate the water of precursor or the precursor of processing substantially all to remove because reach constant weight.
Precursor material is the compound except LMFP, and is the compound that reaction as described herein forms LMFP.Some or all precursor materials can be the sources that two or more must parent material.
Suitable lithium precursor comprises for example lithium hydroxide, lithia, lithium carbonate, lithium dihydrogen phosphate, lithium hydrogen phosphate and phosphoric acidLithium. Lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums and lithium phosphate all serve as lithium ion and HxPO4The source of ion, and canBy forming with lithium hydroxide part neutralising phosphoric acid before combining with all the other precursor materials.
Suitable manganese precursor comprises for example manganese hydrogen phosphate (II) and has manganese (II) compound of fugitive anion. " fugitive " meaningRefer to that material forms one or more volatile byproducts and therefore with gas shape during dry grinding and/or calcining stepFormula is removed from reactant mixture. Volatile byproducts can comprise for example oxygen, water, carbon dioxide, alkane, alcohol or manyTwo or more mixture of unit alcohol, carboxylic acid, polycarboxylic acids or its. The example of fugitive anion for example comprise hydroxide,Oxide, ethanedioic acid root, hydroxyl, carbonate, bicarbonate radical, formate, acetate, there are 18 carbon at the mostOther alkyl salt root of atom, there are 18 carbon atoms at the most polycarboxylic acids radical ion (as citrate, tartrate anionDeng), there is the alkanol radical ion of 18 carbon atoms at the most and there is the glycolic radical ion of 18 carbon atoms at the most. ToolThere is any manganese (II) compound in these fugitive anion to be suitable in this article. Manganese carbonate (II) is preferred manganesePrecursor.
Suitable iron precursor comprises phosphoric acid hydrogen iron (II) and has the iron (II) of any fugitive anion of mentioning in first previous paragraphsCompound. Example comprises ferric carbonate (II), bicarbonate iron (II), ferric formate (II), ferric acetate (II), iron oxide (II), hydroxyl secondAcid iron (II), ferric lactate (II), ironic citrate (II) and tartaric acid iron (II). Ethanedioic acid iron (II) is preferred iron precursor.
Suitable doping metals precursor comprises the compound for example with doping metals and fugitive anion. This suitable class is mixedThe example of assorted metal precursor comprises for example magnesium carbonate, magnesium formate, magnesium acetate, cobalt carbonate (II), cobaltous formate (II) and cobalt acetate(II)。
Suitable HzPO4Ion precursor is except listed above lithium hydrogen phosphate, lithium dihydrogen phosphate and ferric phosphate (II) compoundOutside, also comprise phosphoric acid, phosphoric acid tetraalkyl ammonium compound, phosphoric acid tetraphenyl ammonium compounds, ammonium phosphate, ammonium dihydrogen phosphate (ADP)Deng. It is fugitive that ammonium cation and hydrogen cation tend to, and therefore compares non-fugitive cation (as metal cation)Preferred.
Carbonaceous material or its precursor can be included in the mixture for grinding steps. Suitable carbonaceous material for example comprisesGraphite, carbon black and/or other conductive carbon. Precursor is included in the organic compound that is decomposed to form conductive carbon under calcination reaction condition.These precursors comprise various organic polymers, sugar (as sucrose or glucose) etc.
The preferred mixture of initial substance comprises as the lithium dihydrogen phosphate of the precursor of lithium and phosphate anion, as manganese (II)The manganese carbonate (II) of precursor and as the ethanedioic acid iron (II) of iron (II) precursor.
Precursor is to provide with fine-powder form. Initial particle size is preferably less than 50 microns (as passed through laser diffractometry or lightDiffraction approach is measured) and be preferably no more than 10 microns. If desired, can screen precursor to remove very large particleAnd/or agglomerate.
The product obtaining from dry grinding step is through calcining to form olivine LMFP material or nano-complex. SuitableCalcining heat is 350 DEG C to 750 DEG C and preferably 500 DEG C to 700 DEG C, continues 0.1 to 20 hour and preferably 1 to 4Hour. Alternative condition is to avoid making particles sintering.
Calcining step is to carry out in nonoxidizing atmosphere. The example of nonoxidizing atmosphere comprises nitrogen; The mixing of nitrogen and oxygenThing, wherein oxygen content is less than 1 % by weight, is less than especially by weight 500ppm; Hydrogen, helium, argon gas etc.
During calcining step, fugitive accessory substance is overflowed and the removal of the product from form with gas form. Non-fugitive materialForm olivine LMFP structure. If carbonaceous material or its precursor exist during calcining step, calcining so particle willBe the nano-complex form of olivine material and carbonaceous material. Carbonaceous material may form carbon containing and be coated with on Powdered particleLayer and/or with its formation laminated composites.
If desired, the extent of reaction can operating weight method (it measures the loss of fugitive accessory substance), pass through X-ray diffractionMethod (it indicates the formation of required olivine crystal structure) and/or follow the trail of by other technology. Reaction is preferably proceeded,Until obtain single-phase LMFP material or nano-complex.
The product obtaining from calcining step if desired can be through slight grinding so that aggregation fragmentation. Obtain from calcining stepProduct usually can directly use and without further processing.
Advantage of the present invention is that few during dry grinding and calcining step (if existence) forms very large particle.In the background technology method that has water, tend to form the very large platy particle of fraction. Platy particle is not gentlyUnder micro-grinding, can be easy to be broken into primary particle or less agglomerate compared with the simple aggregation thing of small-particle. In fact, thisIt is the very large primary particle that is not easy disintegration under slight grinding that a little large platy particles tend to. Those platy particlesUsually there is the longest dimension that exceedes 100 microns. It can account at the most 5% of product total amount. In the methods of the invention,The formation of these particles almost (if not completely) is eliminated.
The existence of macroparticle is reflected in D90 and the D99 granularity of dry grinding intermediate and end product. D90 granularity tableShow the size that is equal to or greater than the particle of minimum 90 percents by volume and is less than the particle of maximum 10 percents by volume. D99Granularity represents the large of the particle that is equal to or greater than the particle of minimum 99 percents by volume and is less than maximum 1 percent by volumeLittle.
Compared with the background technology method high with front body water content, dry grinding intermediate of the present invention and LMFP productD90 value usually obviously reduces 25 to 80% or more substantially. D99 value usually reduces equally. For instance, thisBright dry grinding intermediate and the D90 granularity of LMFP product as by laser diffractometry measured, conventionally 10 toIn 60 micrometer ranges. This compares with the value of 50 to 150 microns in background technology method. The D99 granularity of this method is logicalBe everlasting in 50 to 100 micrometer ranges (same as measured by laser diffractometry), with background technology method 150 to500 microns or even more heterogeneous comparison. The content of lower D90 and D99 value instruction macroparticle is much lower.
LMFP material (or nano-complex) constructed in accordance is suitable for makes cathode material. It can be by anySuitable way is formulated in negative electrode, conventionally, by making itself and adhesive fusion, forms slurries and is cast to current-collectorOn. Negative electrode can contain conductive material (as graphite, carbon black, carbon fiber, CNT, metal etc.) particle and/Or fiber.
The relative shortage of macroparticle makes LMFP material of the present invention (and nano-complex) be highly suitable for forming negative electrodeFilm.
Described negative electrode is applicable to lithium battery. The lithium battery that contains this type of negative electrode can have any suitable design. Except the moonOutside the utmost point, this type of battery conventionally comprises anode, is placed in the dividing plate between anode and negative electrode and contacts with negative electrode with anodeElectrolyte solution. Electrolyte solution comprises solvent and lithium salts.
Suitable anode material comprises for example carbonaceous material, as natural or Delanium, carbonization pitch, carbon fiber, graphitePhase microballoon, oven process carbon black, acetylene black and various other graphitized material in the middle of changing. Suitable carbon anodes and for structureThe method of building carbon anodes is described in for example United States Patent (USP) the 7th, in 169, No. 511. Other suitable anode material comprises lithiumMetal, lithium alloy, other lithium compound (as lithium titanate) and metal oxide are (as TiO2、SnO2And SiO2)And as the material of Si, Sn or Sb.
Dividing plate is electrically non-conductive material aptly. Its should be not under operating condition with electrolyte solution or electrolyte solution inAny component reaction or be insoluble in electrolyte solution or electrolyte solution in any component in. Polymerization dividing plate generally closesFit. The example of suitable polymer that forms dividing plate comprise polyethylene, polypropylene, PB Polybutene-1, poly--3-methylpentene,Ethylene-propylene copolymer, polytetrafluoroethylene (PTFE), polystyrene, polymethyl methacrylate, dimethyl silicone polymer, polyethersSulfone etc.
The lithium salt of cell electrolyte solution is at least 0.1 mol/L (0.1M), preferably at least 0.5 mol/L (0.5M), more preferably at least 0.75 mol/L (0.75M), preferably 3 mol/L (3.0M) at the most, and more preferably extremelyMany 1.5 mol/L (1.5M). Lithium salts can be to be suitable for any lithium salts that battery uses, and comprises as LiAsF6、LiPF6、LiPF4(C2O4)、LiPF2(C2O4)2、LiBF4、LiB(C2O4)2、LiBF2(C2O4)、LiClO4、LiBrO4、LiIO4、LiB(C6H5)4、LiCH3SO3、LiN(SO2C2F5)2And LiCF3SO3Lithium salts. Molten in cell electrolyte solutionAgent can be or comprise for example cyclic carbonate alkane diester, as ethyl carbonate; Dialkyl carbonate, as diethyl carbonate, carbonDimethyl phthalate or methyl carbonate ethyl ester; Various alkyl ethers; Various cyclic esters; Various mononitriles; Dintrile, as glutaronitrile; RightClaim or asymmetric sulfone with and derivative; Various sulfolane; There is various organic esters and the ether-ether of 12 carbon atoms at the mostDeng.
Battery is secondary (rechargeable) battery preferably, more preferably serondary lithium battery. In this type of battery, fillElectricity reaction comprises lithium ion from cathode dissolution or goes lithiumation, to electrolyte solution and simultaneously, lithium ion is incorporated to anodeIn. Exoelectrical reaction comprise on the contrary rely on electrolyte solution lithium ion is incorporated to negative electrode from anode.
The battery that contains the negative electrode that comprises lithium transition-metal olivine particle constructed in accordance can be answered for industryWith, as electric motor car, hybrid-power electric vehicle, plug-in hybrid-power electric vehicle, the Aero-Space vehicles and equipment,Electronics bicycle etc. Battery of the present invention is also applicable to operate a large amount of Electrical and Electronic devices, as computer, camera,Video camera, mobile phone, PDA, MP3 and other music player, instrument, TV, toy, video-game player,Household electrical appliance, medical treatment device (as pacemaker and defibrillator) and other.
The lithium battery that contains the negative electrode that comprises LMFP material constructed in accordance shockingly finds to have fabulous appearanceAmount, especially under high charge rate.
The secondary cell that contains the negative electrode that comprises LMFP material of the present invention (, carries out repetition to battery at circulating batteryCharge/discharge cycle) represent afterwards good unexpectedly capability retention, keep specific capacity and high rate performance simultaneously.In secondary (rechargeable) battery, good capability retention with at the long battery life in its recharge and when electric discharge andMore consistent battery performance is relevant. This good capability retention contains in environment temperature (20-25 DEG C) and as usual being everlastingThe slightly high-temperature (40-50 DEG C) that the operating period of the electric device of battery (and being its supplying energy by battery) producesLower visible.
Following instance explanation the present invention is provided, but does not intend to limit its scope. Except as otherwise noted, otherwise all umbersAll be by weight with percentage.
Example 1-3 and comparative sample A and B
Comparative sample A manufactures as follows: by 0.54 part of MnCO3Powder, 0.63 part of LiH2PO4, 0.18 partFe(II)(C2O4)2□2H2O and 0.089 part of KetjenblackEC-600JD carbon black are combined in CM20 high-energy mills (old manThis Co., Ltd (ZozGmbH)) in and grind three hours. Use MicrotrackS3500 laser diffraction granularity to divideAnalyse instrument the sample of gained milled mixtures is carried out to grain size analysis. The D50 of sample is 11.2 μ m, and D90 is 50.6 μ mAnd D99 is 240 μ m. The material of approximately 5 percents by volume is by the large platy particle group of 100 to 1000 μ m sizesBecome. Form graphic through the microphoto of grinding of material samples. In graphic, some large sheets are identified by reference number 1.
Be by being heated to 530 DEG C from room temperature through one hour through milled mixtures, at 530 DEG C, maintain three hours, andThen coolingly through four hours get back to 100 DEG C (they all flow down at flowing nitrogen) and calcine. In the calcining step phaseBetween, water, carbon monoxide and carbon dioxide discharge as fugitive product. Measure as previously mentioned the grain through calcined productDegree distributes. D50, the D90 of this material and D99 are respectively 15.3,101 and 362 μ m.
Through calcined materials be by make its with carbon fiber and poly-(vinylidene fluoride) with the solid weight of 93: 2: 5 than together with pulpAnd formation negative electrode. On aluminium foil, pass through slurries drawing-down and cast membrane. Film is dry overnight at 80 DEG C. Then by desciccator diaphragmPunching is to manufacture electrode discs. Disk is with thickness sign and through weighing with calculated activity material useful load. Then, willDisk is compressed to 1.3-1.5gm/cm3The active material of target density, and dry overnight at 150 DEG C under vacuum.Assemble the big Lip river of generation gram (Swagelok) battery and be placed on equine (Maccor) cell tester and carry out electrochemistry surveyAmount.
Under constant 1C speed, battery is charged to 4.25V voltage. Battery then discharges under 4.25V, until electric currentTill decaying to C/100. Battery then discharges under different rates, until voltage drops to 2.7V. Each electric dischargeAfter be charged to 4.25V completely. Discharge rate is sequentially C/10, C10,1C, 5C, C/10 and C/10. At 5C andCalculated capacity under C/10 discharge rate. C/10 discharge capacity is that 137mAh/g and 5C discharge capacity are 97mAh/g.
For forming comparative sample B, by a part mentioned above through milled mixtures via the screening of US400 eye mesh screen withRemove large sheet. Be 10.3 μ m through the D50 of screening materials, D90 is that 28.5 μ m and D99 are 60 μ m. WarpScreening materials is then calcined in the mode identical with comparative sample A, and through calcined materials equally with comparative sample AIdentical mode forms electrode and is tested. Result is as indicated in table 1.
Except precursor material is all dried 16 hours separately in combination and before grinding at 105 DEG C, example 1 isForm in the mode identical with comparative sample A.
Except precursor all sieved via US400 eye mesh screen and is then dried 16 at 105 DEG C before grinding stepsOutside hour, example 2 is to form in the general mode identical with comparative sample A.
Except precursor before grinding steps at 105 DEG C dry 16 hours, and through grinding-material before calcining stepOutside the screening of US400 eye mesh screen, example 3 is to form in the general mode identical with comparative sample A.
The granularity data of each in example 1-3 and electrochemical data are to obtain in the mode described in comparative sample A.Result is as indicated in table 1.
Table 1
ND-undetermined. * be not example of the present invention.
The benefit of drying steps is carried out in data acknowledgement in table 1 according to the present invention. Compared with comparative example, example 1-3 existsSpecific capacity under C/10 is slightly higher, but the difference of seeing highly significant under higher (5C) discharge rate. ExampleThe specific capacity of 1-3 under 5C discharge rate is roughly high by 15%.
The higher capacity of example 1-3 is not merely the result that affects of granularity. This is that the result obtaining by example 1 is brightConfirmation is real, and it has remarkable larger granularity compared with comparative sample B*, but performance is significantly better. Example 1 also withExample 2 and 3 performances are suitable, but example 2 and 3 has much smaller granularity.
Example 4-6 and comparative sample C
Comparative sample C: the LMFP formula LiMn that sees service0.8Fe0.2PO4LMFP/ carbon nano-complex be by as closeIn described in previous example in the CM20 high-energy mills from Sou Si Co., Ltd dry grinding LiH2PO4、MnCO3、Fe(C2O4)□2H2Prepared by the mixture of O and KetjenblackEC-600JD carbon black. Then, as previouslyDescribed in example, calcining is through grinding-material. Through calcined product formation negative electrode as discussed previously. Enter in previously described general modeRow electrical testing.
Except precursor was dried 16 hours separately before dry grinding step at 105 DEG C, example 4 is with phase TongfangFormula is manufactured and test.
Except the anhydrous ethanedioic acid iron displacement of ethanedioic acid iron dihydrate with equimolar amounts, example 5 be with comparison specimenThe mode that product C is identical is manufactured and is tested.
Except precursor before dry grinding step at 105 DEG C separately dry 16 hours, example 6 be with example6 identical modes are manufactured and are tested.
The result of electro-chemical test is indicated in table 2.
Table 2
* be not example of the present invention.
Find out example 4-6 under 1C and 5C discharge rate and the tool under the C/10 speed after circulation second and the 7thHave significantly compared with height ratio capacity (with respect to comparative sample C).
Example 7-9 and comparative sample D
Comparative sample D: the LMFP formula Li that sees service1.025Mn0.8Fe0.2PO4LMFP/ carbon nano-complex be to pass throughAs described in about previous example in the CM20 high-energy mills from Sou Si Co., Ltd dry grinding LiH2PO4、MnCO3、Fe(C2O4)□2H2Prepared by the mixture of O and KetjenblackEC-600JD carbon black. Then, at porcelain earthenwareIn crucible, at 530 DEG C, calcine 100 grams through grinding-material 3 hours. Through calcined product formation negative electrode as discussed previously. To closeCarry out electro-chemical test in the general mode described in example 4-6.
Except precursor before dry grinding step at 105 DEG C separately dry 16 hours and through grinding-material in calciningFront via outside the screening of US400 eye mesh screen, example 7-9 manufactures in the same manner and tests. Calcining is in groupIn heat department (Pyrex) dish, carry out with 750 grams of batches. Electro-chemical test is to enter in the mode identical with comparative sample DOK.
Result is as indicated in table 3.
Table 3
* be not example of the present invention.
Example 7-9 represents the capacity more much bigger than comparative sample D, especially under 1C, 5C and 10C discharge rate.
Example 10 and 11 and comparative sample E and F
The LMFP formula Li that sees service1.025Mn0.8Fe0.2PO4LMFP/ carbon nano-complex be by as about previous realityExample described in the CM20 high-energy mills from Sou Si Co., Ltd dry grinding LiH2PO4、MnCO3、Fe(C2O4)□2H2Prepared by the mixture of O and KetjenblackEC-600JD carbon black. In roller kilns simulator, calcineThrough milled mixtures. This equipment has the saggar that holds sample in the time of calcining. For comparative sample F, saggar 3.6kgFill through grinding-material. At 530 DEG C, calcine 3 hours. By the sample obtaining from saggar top and bottom for electricityTest chemical. In the general mode about described in example 7-9 to carrying out electro-chemical test through calcined materials.
Only use 1.8kg through grinding precursor filling except the saggar of kiln simulator, comparative sample F makes in the same mannerMake and test.
Except precursor at 105 DEG C separately dry 3 hours and through grind precursor before calcining via US400 eye mesh screenOutside screening, example 10 is to manufacture and test in the mode identical with comparative sample E.
Except the anhydrous ethanedioic acid iron displacement of ethanedioic acid iron dihydrate with equimolar amounts, example 11 be with relativelyThe mode that sample E is identical is manufactured and is tested.
The result of electro-chemical test is as indicated in table 4.
Table 4
Comparative sample E and F show that using conventional precursor to realize powder loads. In comparative sample E, from saggar topAnd between the sample that obtains of bottom, find out the very big variation of specific capacity. By making useful load reduce by 50% (comparative sample F),Likely obtain more consistent product, but production capacity loss is larger. Use background technology material must be far below equipmentCapacity operates to obtain whole batch of subuniform product quality. Example 10 and 11 shows when warp used according to the inventionWhen dried precursor, even if still obtain much better all the time product under large Production Batch Size.

Claims (12)

1. for the manufacture of mechanochemistry/solid-state approach of LMFP cathode material, described method comprises:
A) dry grinding water content is less than the mixture of the precursor particles of 1 % by weight, and described precursor particles comprises necessarilyBefore at least one lithium precursor, at least one manganese (II) precursor, at least one iron (II) precursor and at least one phosphate of amountBody, optionally carbonaceous material or its precursor and optionally have the doping metals precursor of fugitive anion, rub to provide oftenThe manganese (II) of your phosphate anion 0.85 to 1.15 mole of lithium and 0.95 to 1.05 mole of combination of every mole of phosphoric acid radical ion,Iron (II) and doping metals; And
B) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
2. method according to claim 1, the water content of wherein said precursor particles is less than 0.25 % by weight.
3. method according to claim 2, the water content of wherein said precursor particles is less than 0.1 % by weight.
4. for the manufacture of mechanochemistry/solid-state approach of LMFP cathode material, described method comprises:
A) dry at least one lithium precursor, at least one manganese (II) precursor, at least one iron (II) precursor and at least of comprisingA kind of phosphate precursor, optionally carbonaceous material or its precursor and optionally there is the doping metals precursor of fugitive anionPrecursor particles be less than 1 % by weight so that the water content of described precursor is reduced to;
B) mixture of a certain amount of described dried precursor particle of dry grinding, to provide every mole of phosphoric acid radical ion 0.85To manganese (II), iron (II) and the doping metals of 1.15 mole of lithium and 0.95 to 1.05 mole of combination of every mole of phosphoric acid radical ion;And
C) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
4. method according to claim 3, wherein step a) in, described precursor drying is so that described precursorWater content be reduced to and be less than 0.25 % by weight.
5. method according to claim 3, wherein step a) in, described precursor drying is so that described precursorWater content be reduced to and be less than 0.1 % by weight.
6. for the manufacture of mechanochemistry/solid-state approach of LMFP cathode material, described method comprises:
A) dry grinding comprises a certain amount of at least one lithium precursor, at least one manganese (II) precursor, at least one is anhydrousIron (II) precursor and at least one phosphate precursor, optionally carbonaceous material or its precursor and optionally have fugitive the moon fromThe precursor particles of the doping metals precursor of son, to provide every mole of phosphoric acid radical ion 0.85 to 1.15 mole of lithium and often to rubManganese (II), iron (II) and the doping metals of 0.95 to 1.05 mole of combination of your phosphate anion; And
B) under nonoxidizing atmosphere, calcine gained polishing particles mixture, to form olivine LMFP powder.
7. according to method in any one of the preceding claims wherein, wherein said lithium precursor comprises lithium dihydrogen phosphate, phosphoric acidOne or more in hydrogen two lithiums and lithium phosphate.
8. according to method in any one of the preceding claims wherein, wherein said manganese (II) precursor is to have fugitive anionManganese (II) compound.
9. method according to claim 8, wherein said manganese (II) precursor is manganese carbonate (II).
10. according to method in any one of the preceding claims wherein, wherein said iron (II) precursor is to have fugitive anionIron (II) compound.
11. methods according to claim 10, wherein said iron (II) precursor is ethanedioic acid iron (II).
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